Brown copper containing aromatic amine-sulphur dyes and process of making the same



Patented Apr. 13, 1926.

UNITED STATES PATENT OFFICE.

aosnrn rnncnsmmrnm m mum L. nunen'ss, or wnmine'ron, nntawaan, nssrenonsT0 E. I. no 20m Dnmmouns a conramr, or wrmrmeron', DELA- WARE, ACORPORATION 03' DELAW ARE. y

BROWN COPPER CONTAINING ABOHATIG MINE-SULPHUR D'YES AND PROCESS 01'MAKING THE SAME.

No Drawing.

To all whom it may cmwe'm:

Be it known that we, Josnrn FLACHS- 'LAENDER and LAURIE L. Bunonss,citizen of,

Germany and subject of the King of England, a nd residents ofWilmington, in the county of New Castle and State of. Delaware, haveinvented a certain new and useful Brown Copper Containing AromaticAmine-Sulphur Dyes and Processes of Making the Same, of which thefollowing is a specification.

This invention relates to the production of sulphur dyes of from brownto khaki shades, and comprises heating together an aromatic amine andsul hur, dissolving the resulting mass in so ium hydroxide or sodiumsulphide solution, incorporating a compound of copper in the resultingsolution, and then evaporating the mixture to dryness. Proceeding inthis manner, a full cutch shade is produced which cannot be obtainedwhen the copper salts are omitted.

For the amine there may be used a diamine such as toluylenediamine, or amixture thereof with a nitroamine such as paranitraniline. As coppersalts there may be used the sulphates, chlorides, etc. of copper.

The process for manufacturing these dyestufi's is illustrated by thefollowing example:

500 pounds of sulpur are charged into an iron thionator provided with anagitator, the temperature raised to 160 C. and maintained at about thatpoint until the sulphur is all melted. 150 ounds of mtoluylenediamine isthen adde quickly. The

temperature is then raisedin about'4 hours to-275 C. and maintained atthis point for 18 to 22' hours, or until the desired shade and maximumstrength have been develo ed. The charge is. then cooled to 180 and 1350pounds of a thirtyper cent solution of sodium hydroxide added.Theresulting mass is boiled until sulphur compound is compl'eteldissolved, and 40 ounds of copper sulp ate crystals added. he resultingmixture is then evaporated to'dryness, maintaining the temperature atabout 230 'C. until water ceases to i be evolved. Then 200 pounds ofsalt are added and the temperature raised to 295 C. during the course of4 to 6' hours and held at this temperature for about 4 hours or untilalkaline solution 0 diamine of the benzenoid series, evaporating thesolution to dryness and bakin the resi- Applicatlon filed larch 19,1924. Serial No. 700,379.

a test shows thatthe desired shade and.

maximum strength have been obtained. It is then cooled, discharged andground. The dyestufiobtained by this process is easily soluble in hotdilute sodium h droxi'de or sodium sulphide "solutions an dyesunmordanted cotton in full cutch shades which are fast to washing,milling and acids.

Our process is not, of course, limited to caustic, evaporated and bakedwith theaddi-,

tion of copper sulphate, a dye of khaki shade is produced. I

here maybe considerable variation in times and temperatures given in theabove example. For instance, the temperature in the final baking may belowered from 295 to 280, in whlch case a dye appreciably yellower inshade is od uced term baking as u herein, we mean heating at atemperature in the neighborhood of, but usually a little below, 300 C.

The cepper compound referred to above may, if actlon mass duringthionation of the aromatic diamine. I

' We claim: i

' 1. The process of making sulphur dyes of from brown to khaki shadeswhich comprises incorporatin a copper salt in an alka- By the 1 esired,be introduced into there line solution of a t ionated aromatic amine,

evaporating the solution to dryness, and bakin the dried mass until aproduct of suitab e shade and strength is obtained.

2. The process of making sulphur dyes of from brown to khaki shadeswhich comprises mixing-a copper salt with an aqueous a thionatedaromatic due until a product of suitable s ade and strength is obtained.

3 he process of making sulphur dyes of from brown to khaki shadeswhich'comprises mixing a copper salt with a sodium ydroxide solution ofa. thionated metatoluylenediamine, evaporating the solution to drynessand baking the residue until a product of suitable shade and strength isobtained.

4. A process as set forth in claim 1 in which the baking is carried onat a temperature of from about 280 to 295 C.

5. The process of making sulphur dyes of from brown to -khaki shadeswhich comprises heating a mixture comprising metatoluylenediamineandsulphur until a prodnot of the desired shade and strength is formed,dissolving the reaction mass in sodium hydroxide solution, adding asoluble copper salt to resulting solution, evaporating the mixture todryness and baking the residue until a product of the desired shade andstrength is obtained.

6. A process as set forth in claim 5 in which the thionation of themeta-toluylenediamine is effected at a temperature of about 275 (1., andthe-baking of the residue is done at a temperature of from about 280 to295 C. I

- tainable by incorporating a copper salt in an alkaline solution of athionated' aromatic amine, evaporatin the solution to dryness, andbaking the dr ed mass until a product and acids.

11. As a new product a sulphur dye obtainable by mixing a copper saltwlth an aqueous al aline solution of a thionated aromatic diamine of thebenzenoid series, evaporating the solution to dryness, and baking theresidue until a product of suitable shade and strength is produced, saidsulphur dye being easily soluble in hot dilute sodium hydroxide orsodium sulphide solutions, and

dyeing unmordanted cotton in from brown to khaki shades which are fastto washing, milling, and acids.

12. As anew product a sulphur dye obtainable by mixing a copper saltwith a sodium hydroxide solution of a thionated meta-toluylenediamine,evaporating the solution to dryness, and baking the residue untilaproduct of suitable shade and strength is produced, said sulphur dyebeing easily soluble in hot dilute sodium hydroxide or sodium sulphidesolutions, and dyeing unmordanted cotton in from brown to khaki shadeswhich are fast to washing, milling, and acids.

13. As a new product the sulphur dye obtainable by the process set forthin claim 4.

14. As a new product the sulphur dye obtainable by the process set forthin claim 5.

15. As a new product the sulphur dye obtainable by the process set forthin claim 7.

In testimony whereof we aflix our signatures.

JOSEPH FLACHSLAENDER. LAURIE L. BURGESS

